Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
  • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
  • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
  • C08G65/14—Unsaturated oxiranes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
  • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
  • C08G65/24—Epihalohydrins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M6/00—Primary cells; Manufacture thereof
  • H01M6/14—Cells with non-aqueous electrolyte
  • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
  • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M10/00—Secondary cells; Manufacture thereof
  • H01M10/05—Accumulators with non-aqueous electrolyte
  • H01M10/052—Li-accumulators
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present invention relates to a crosslinkable polyether copolymer, a crosslinked material of the copolymer, and a crosslinked solid polyelectrolyte. More particularly, the present invention relates to a solid polyelectrolyte which is suitable as a material for an electrochemical device such as a battery, a capacitor and a sensor.
• an electrolyte constituting an electrochemical device such as a battery, a capacitor and a sensor
• those in the form of a solution or a paste have hitherto been used in view of the ionic conductivity.
• the following problems are pointed out.
• a solid electrolyte such as an inorganic crystalline substance, inorganic glass, and an organic polymer substance is suggested.
• the organic polymer substance is generally superior in processability and moldability and the resulting solid electrolyte has good flexibility and bending processability and, furthermore, the design freedom of the device to be applied is high and, therefore, the development thereof is expected.
• the organic polymer substance is inferior in ionic conductivity to other materials at present.
• a polymer solid electrolyte prepared by crosslinking a polymer compound having average molecular weight of from 1,000 to 20,000 shows a comparatively good ionic conductivity within the practical temperature range, but those having more excellent mechanical characteristics and ionic conductivity are required.
• a polyether copolymer having an oligooxyethylene side chain described in Japanese patent Application No. 109616/1995 of the present applicant shows excellent ionic conductivity at room temperature (e.g. 30°C).
• room temperature e.g. 30°C
• temperature e.g. 60°C
• plastic deformation e.g., when using in a thin type battery, there is a fear of a short circuit between a positive electrode and a negative electrode.
• An object of the present invention is to provide a solid electrolyte, which is superior in ionic conductivity, and which causes no plastic deformation or has no fluidity even under high temperature.
• Another object of the present invention is to provide a polymer, which gives the above solid electrolyte.
• the present invention provides a polyether copolymer having a number-average molecular weight of 50,000 to 2,000,000, a glass transition temperature measured by a differential scanning calorimeter (DSC) of not more than -60°C and a fusion heat of not more than 70 J/g, comprising:
• the present invention also provides a crosslinked material obtained by crosslinking the above copolymer.
• the present invention provides a solid polyelectrolyte comprising the above crosslinked material and an electrolyte salt compound.
• the present invention provides a battery comprising said solid polyelectrolyte.
• the repeating unit (C) may be derived from a monomer of the formula (III-1) or (III-2): wherein R 2 and R 3 represent a reactive functional group-containing group.
• the polymer of the present invention comprises (A) a repeating unit derived from a monomer of the formula (I): wherein R 1 is a group selected from an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, an aralkyl group having 7 to 12 carbon atoms and a tetrahydropyranyl group,
• the repeating unit (C) derived from a monomer of the formula (III-1) or (III-2) is represented by the formula (III'-1) or (III'-2): wherein R 2 and R 3 represent a reactive functional group-containing group.
• the reactive functional group in the repeating unit (C) is preferably (a) a reactive silicon group, (b) an epoxy group, (c) an ethylenically unsaturated group, or (d) a halogen atom.
• the polymerization method of the polyether copolymer having a crosslinkable side chain of the present invention is conducted in the same manner as in Japanese Patent Kokai Publication Nos. 154736/1988 and 169823/1987 of the present applicant.
• the polymerization reaction can be conducted as follows. That is, the polyether copolymer can be obtained by reacting the respective monomers at the reaction temperature of 10 to 80°C under stirring, using a catalyst mainly composed of an organoaluminum, a catalyst mainly composed of an organozinc, an organotin-phosphate ester condensate catalyst and the like as a ring opening polymerization catalyst in the presence or absence of a solvent.
• the organotin-phosphate ester condensate catalyst is particularly preferable in view of the polymerization degree or properties of the resulting copolymer.
• the reaction functional group does not react and a copolymer having the reaction functional group is obtained.
• the content of the repeating unit (A) is from 1 to 98% by mol, preferably from 3 to 98% by mol, e.g. from 5 to 90% by mol; the content of the repeating unit (B) is from 95 to 1% by mol, preferably from 95 to 1% by mol, e.g. from 90 to 5% by mol; and the content of the repeating unit (C) is from 0.005 to 10% by mol, preferably from 0.01 to 5% by mol, e.g. from 0.05 to 5% by mol.
• the content of the repeating unit (B) exceeds 95% by mol, an increase in glass transition temperature and crystallization of the oxyethylene chain arise, which results in drastic deterioration of the ionic conductivity of the solid electrolyte. It is generally known that the ionic conductivity is improved by the decrease of the crystallizability of polyethylene oxide. It has been found that, in case of the polyether copolymer of the present invention, the effect for improvement of the ionic conductivity is remarkably large.
• the molar ratio of the repeating unit (C) is smaller than 0.005% by mol, the copolymer can not be sufficiently crosslinked and, therefore, it is difficult to obtain a solid electrolyte at high temperature range (e.g. 60°C).
• the molar ratio of the repeating unit (C) is larger than 15% by mol, it becomes impossible to form a film.
• the glass transition temperature and fusion heat of the polyether copolymer are measured by a differential scanning calorimeter (DSC).
• DSC differential scanning calorimeter
• the glass transition temperature of the polyether copolymer is not more than -60°C, preferably not more than -63°C, e.g. not more than -65°C.
• the fusion heat of the polyether copolymer is not more than 70 J/g, e.g. not more than 60 J/g, particularly not more than 50 J/g.
• the polyether copolymer of the present invention may be any copolymer type such as a block copolymer and a random copolymer, but the random copolymer is preferable because the effect for reduction of the crystallizability of polyethylene oxide is large.
• the polyether copolymer of the present invention is a polyether copolymer having an oligooxyethylene side chain and a side chain containing a crosslinkable reactive functional group.
• the polyether copolymer of the present invention is normally a terpolymer formed from three monomers, but it may be a copolymer formed from at least four monomers.
• the monomer having a reactive silicon group, which constitutes the repeating unit (C), is preferably represented by the formula (III-a-1): wherein R 2 is a reactive silicon group-containing group, or the formula (III-a-2): wherein R 3 is a reactive silicon-containing group.
• the reactive silicon group-containing monomer represented by the formula (III-a-1) is preferably a compound represented by the formula (III-a-1-1) or (III-a-1-2).
• the reactive silicon group-containing monomer represented by the formula (III-a-2) is preferably a compound represented by the formula (III-a-2-1).
• R 4 , R 5 and R 6 may be the same or different, but at least one of them represents an alkoxy group and the remainder represents an alkyl group; and m represents 1 to 6.
• Examples of the monomer represented by the formula (III-a-1-1) include 1-glycidoxymethyltrimethoxysilane, 1-glycidoxymethylmethyldimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 4-glycidoxybutylmethyldimethoxysilane, 4-glycidoxybutylmethyltrimethoxysilane, 6-glycidoxyhexylmethyldimethoxysilane and 6-glycidoxyhexylmethyltrimethoxysilane.
• Examples of the monomer represented by the formula (III-a-1-2) include 3-(1,2-epoxy)propyltrimethoxysilane, 3-(1,2-epoxy)propylmethyldimethoxysilane, 3-(1,2-epoxy)propyldimethylmethoxysilane, 4-(1,2-epoxy)butyltrimethoxysilane, 4-(1,2-epoxy)butylmethylditrimethoxysilane, 5-(1,2-epoxy)pentyltrimethoxysilane, 5-(1,2-epoxy)pentylmethyldimethoxysilane, 6-(1,2-epoxy)hexyltrimethoxysilane and 6-(1,2-epoxy)hexylmethyldimethoxysilane.
• Examples of the monomer represented by the formula (III-a-2-1) include 1-(3,4-epoxycyclohexyl)methyltrimethoxysilane, 1-(3,4-epoxycyclohexyl) methylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 3-(3,4-epoxycyclohexyl) propyltrimethoxysilane, 3-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane, 4-(3,4-epoxycyclohexyl)butyltrimethoxysilane and 4-(3,4-epoxycyclohexyl) butylmethyldimethoxysilane.
• 3-glycidoxypropyltrimethoxysilane 3-glycidoxypropylmethyldimethoxysilane, 4-(1,2-epoxy)butyltrimethoxysilane, 5-(1,2-epoxy)pentyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are particularly preferable.
• the monomer having two epoxy groups, which constitutes the repeating unit (C), is preferably represented by the formula (III-b): wherein R 7 is a divalent organic group.
• the monomer having two epoxy groups is preferably a compound represented by the following formula (III-b-1), (III-b-2) or (III-b-3):
• a 1 and A 2 represent a hydrogen atom or a methyl group; and m represents a numeral of 0 to 12.
• Examples of the monomer represented by the formula (III-b-1) include 2,3-epoxypropyl-2',3'-epoxy-2'-methyl propyl ether, ethylene glycol-2,3-epoxypropyl-2',3'-epoxy-2'-methyl propyl ether, and diethylene glycol-2,3-epoxypropyl-2',3'-epoxy-2'-methyl propyl ether.
• Examples of the monomer represented by the formula (III-b-2) include 2-methyl-1,2,3,4-diepoxybutane, 2-methyl-1,2,4,5-diepoxypentane, and 2-methyl-1,2,5,6-diepoxyhexane.
• Examples of the monomer represented by the formula (III-b-3) include hydroquinone-2,3-epoxypropyl-2',3'-epoxy-2'-methyl propyl ether and catechol-2,3-epoxypropyl-2',3'-epoxy-2'-methyl propyl ether.
• 2,3-epoxypropyl-2',3'-epoxy-2'-methyl propyl ether and ethylene glycol-2,3-epoxypropyl-2',3'-epoxy-2'-methyl propyl ether are particularly preferable.
• the monomer having the ethylenically unsaturated group, which constitutes the repeating unit (C), is preferably represented by the formula (III-c): wherein R 8 is a group having an ethylenically unsaturated group.
• allyl glycidyl ether 4-vinylcyclohexyl glycidyl ether, ⁇ -terpinyl glycidyl ether, cyclohexenylmethyl glycidyl ether, p-vinylbenzyl glycidyl ether, allylphenyl glycidyl ether, vinyl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentane, 1,2-epoxy-5,9-cyclododecadiene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl
• Preferable examples thereof include ally glycidyl ether, glycidyl acrylate and glycidyl methacrylate.
• the monomer (C) having a halogen atom is preferably represented by the formula (III-d): wherein R 9 is a group having at least one halogen atom.
• Examples of the monomer having a halogen atom include: wherein X is a halogen atom, particularly a bromine atom (Br) or an iodine atom (I).
• the polymerization degree n of the oxyethylene unit of the side chain portion in the monomer (I), which constitutes the repeating unit (A), is preferably from 1 to 12, e.g. 1 to 6. When the polymerization degree n exceeds 12, the ionic conductivity of the resulting polymer solid electrolyte is deteriorated, unfavorably.
• R 1 may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an ally group or a cyclohexyl group.
• the number-average molecular weight of the polyether copolymer is suitable within the range from 50,000 to 2,000,000, preferably from 100,000 to 2,000,000, so as to obtain excellent processability, moldability, mechanical strength and flexibility.
• the number-average molecular weight is smaller than 50,000, it is necessary to increase the crosslink density so as to maintain the mechanical strength or to prevent from flowing at high temperature, which results in deterioration of ionic conductivity of the resulting electrolyte.
• it exceeds 2,000,000 the processability and moldability become insufficient.
• the crosslinking can be conducted by the reaction between the reactive silicon group and water.
• organometal compounds for example, tin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and dibutyltin acetylacetonate; titanium compounds such as tetrabutyl titanate and tetrapropyl titanate; aluminum compounds such as aluminum trisacetyl acetonate, aluminum trisethyl acetoacetate and diisopropoxyaluminum ethylacetoacetate; or amine compounds such as butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triety
• the reactive functional group is an epoxy group
• polyamines and acid anhydrides can be used.
• polyamines examples include aliphatic polyamines such as diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, hexamethylenediamine, N-aminoethylpiperazine, bis-aminopropylpiperazine, trimethylhexamethylenediamine and dihydrazide isophthalate; and aromatic polyamines such as 4,4'-diamino diphenyl ether, diamino diphenyl sulfone, m-phenylenediamine, 2,4-toluylenediamine, m-toluylenediamine, o-toluylenediamine and xylylenediamine.
• the amount of the polyamine varies depending on the type of the polyamine, but is normally within the range from 0.1 to 10% by weight based
• Examples of the acid anhydrides includes maleic anhydride, dodecenylsuccinic anhydride, chlorendic anhydride, phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylenemaleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride and trimellitic anhydride.
• the amount of the acid anhydrides varies depending on the type of the acid anhydride, but is normally within the range from 0.1 to 10% by weight based on the whole composition. In the crosslinking, an accelerator can be used.
• the accelerator include phenol, cresol, resorcin, pyrogallol, nonyl phenol and 2,4,6-tris(dimethylaminomethyl)phenol.
• the accelerator include benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 2-(dimethylaminoethyl)phenol, dimethylaniline and 2-ethyl-4-methylimidazol.
• the amount of the accelerator varies depending on the type of the accelerator, but is normally within the range from 0.1 to 10% by weight based on the crosslinking agent.
• a radical initiator selected from an organic peroxide, an azo compound and the like, or active energy ray such as ultraviolet ray and electron ray is used. It is also possible to use a crosslinking agent having silicon hydride.
• organic peroxide there can be used those which are normally used in the crosslinking, such as ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide and peroxy ester.
• ketone peroxide peroxy ketal
• hydroperoxide dialkyl peroxide
• diacyl peroxide and peroxy ester.
• Specific examples thereof include methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,2-bis(t-butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-buty
• azo compound there can be used those which are normally used in the crosslinking, such as an azonitrile compound, an azoamide compound and an azoamidine compound, and specific examples thereof include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethyl-valeronitrile, 2,2-azobis(2-methyl-N-phenylpropionamidine)dihydrochloride, 2,2'-azobis[N-(4-chlorophenyl)-2-methylpropionamidine]dihydrochloride, 2,2'-azobis[N-hydroxyphenyl
• glycidyl acrylate ether In the crosslinking due to radiation of activated energy ray such as ultraviolet ray, glycidyl acrylate ether, glycidyl methacrylate ether and glycidyl cinnamate ether are particularly preferable among the monomer component represented by the formula (III-c).
• acetophenones such as diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxy-ethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl-phenylketone and 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one; benzoin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenones such as benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, hydroxybenz
• auxiliary crosslinking agent for crosslinking reaction by ultraviolet ray there can be optionally used ethylene glycol diacrylate, ethylene glycol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, oligopropylene glycol diacrylate, oligopropylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,3-glycerol dimethacrylate, 1,1,1-trimethylolpropane dimethacrylate, 1,1,1-trimethylolethane diacrylate, pentaerythritoltrimethacrylate, 1,2,6-hexanetriacrylate, sorbitol pentamethacrylate, methylenebisacrylamide, methylenebismethacrylamide divinyl benzene, vinyl methacrylate, vinyl crotonate, vinyl
• the compound having silicon hydride which is used for crosslinking the ethylenically unsaturated group
• a compound having at least two silicon hydrides are used.
• a polysiloxane compound or a polysilane compound is preferable.
• Examples of the polysiloxane compound include a linear polysiloxane compound represented by the formula (a-1) or (a-2), or a cyclic polysiloxane compound represented by the formula (a-3).
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 respectively represent a hydrogen atom or an alkyl or alkoxy group having 1 to 12 carbon atoms; and n ⁇ 2, m ⁇ 0, 2 ⁇ n + m ⁇ 300 .
• the alkyl group a lower alkyl group such as a methyl group and an ethyl group is preferable.
• As the alkoxy group a lower alkoxy group such as a methoxy group and ethoxy group is preferable.
• silane compound a linear silane compound represented by the formula (b-1) can be used.
• R 20 , R 21 , R 22 , R 23 and R 24 respectively represent a hydrogen atom or an alkyl or alkoxy group having 1 to 12 carbon atoms; and n ⁇ 2, m ⁇ 0, 2 ⁇ m + n ⁇ 100 .
• Examples of the catalyst of the hydrosilylation reaction include transition metals such as palladium and platinum or a compound or complex thereof. Furthermore, peroxide, amine and phosphine can also be used. The most popular catalyst includes dichlorobis(acetonitrile)palladium(II), chlorotris(triphenylphosphine)rhodium(I) and chloroplatic acid.
• a crosslinking agent such as polyamienes, mercaptoimidazolines, mercaptopyrimidines, thioureas and polymercaptanes can be used.
• polyamines examples include hexamethylenediamine carbamate, triethylenetetramine, tetraethylenspentamine, ethylenediamine carbamate, diethylenetriamine, dipropylenetriamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, hexamethylenediamine, trimethylhexamethylenediamine, diaminophenyl sulfone, m-phenylenediamine, 2,4-toluylenediamine, m-toluylenediamine, o-toluylenediamine, and xylylenediamine.
• Examples of the mercaptoimidazolines include 2-mercaptoimidazoline, 4-methyl-2-mercaptoimidazoline, and 5-ethyl-4-butyl-2-mercaptoimidazoline.
• Examples of the mercaptopyrimidines include 2-mercaptopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, and 5-butyl-2-mercaptopyrimidine.
• Examples of the thioureas include thiourea, ethylene thiourea, dibutyl thiourea, trimethyl thiourea, triethyl thiourea, and tributyl thiourea.
• polymercaptanes examples include 2-dibutylamino-4,6-dimethylcapto-s-triazine, 2-phenylamino-4,6-dimercaptotriazine, 2,5-dimercapto-1,3,4-thiazole, 1,10-decanedithiol, 2,3-dimercaptopyrazine, 2,3-dimercaptoquinoxaline, and 6-methylquinoxaline-2,3-dithiocarbonate.
• the amount of the crosslinking agent varies depending on the type of the crosslinking agent, but is normally within the range from 0.1 to 30% by weight based on the whole composition.
• a metal compound as an acid acceptor is effective to add to the composition of the present invention in view of the thermal stability of the halogen-containing polymer.
• the metal oxide as the acid acceptor include oxide, hydroxide, carbonate, carboxylate, silicate, borate, and phosphite of Group II metals of the Periodic Table; and oxide, basic carbonate, basic carboxylate, basic phosphite, basic sulfite, or tribasic sulfate of Group VIa metals of the Periodic Table.
• magnesia magnesium hydroxide, barium hydroxide, magnesium carbonate, barium carbonate, quick lime, slaked lime, calcium carbonate, calcium silicate, calcium stearate, zinc stearate, calcium phthalate, magnesium phosphite, calcium phosphite, zinc white, tin oxide, litharge, read lead, white lead, dibasic lead phthalate, dibasic lead carbonate, tin stearate, basic lead phosphite, basic tin phosphite, basic lead sulfite, and tribasic lead sulfate.
• the amount of the metal compound as the above acid acceptor varies depending on the type thereof, but is normally within the range from 0.1 to 30% by weight based on the whole composition.
• the electrolyte salt compound used in the present invention is preferably soluble in a polyether copolymer of the present invention or a crosslinked material of said copolymer.
• the following salt compounds are preferably used.
• examples thereof include a compound composed of a cation selected from a metal cation, ammonium ion, amidinium ion and guanidium ion, and an anion selected from chlorine ion, bromine ion, iodine ion, perchlorate ion, thiocyanate ion, tetrafluoroborate ion, nitrate ion, AsF 6 - , PF 6 - , stearylsulfonate ion, octylsulfonate ion, dodecylbenzenesulfonate ion, naphthalenesufonate ion, dodecylnaphthalenesulfonate ion, 7,7,8,8-tetracyano-p-quinodimethane ion, X 1 SO 3 - , (X 1 SO 2 )(X 2 SO 2 )N - , (X 1
• X 1 , X 2 and X 3 independently represent a perfluoroalkyl or perfluoroaryl group having 1 to 6 carbon atoms and Y represents a nitro group, a nitroso group, a carbonyl group, a carboxyl group or a cyano group.
• X 1 , X 2 and X 3 may be the same or different.
• the metal cation a cation of a transition metal can be used.
• a cation of a metal selected from Mn, Fe, Co, Ni, Cu, Zn and Ag metals is used.
• a cation of a metal selected from Li, Na, K, Rb, Cs, Mg, Ca and Ba metals good results are also obtained.
• Two or more compounds described above may be used as the electrolyte salt compound.
• the amount of the electrolyte salt compound is so that a value of a molar ratio of the number of moles of the electrolyte salt compound to the total number of moles of oxyethylene units (the total number of moles of oxyethylene units included in a main chain and side chain of the polyether copolymer) is preferably within the range from 0.0001 to 5, more preferably from 0.001 to 0.5.
• this value exceeds 5, the processability and moldability, the mechanical strength and flexibility of the resulting solid electrolyte are deteriorated, and, furthermore, ionic conductivity is also deteriorated.
• a flame retardant When using the polyether copolymer of the present invention, its crosslinked material, and crosslinked polymer solid electrolyte obtained from them, a flame retardant can be used when the flame retardance is required. That is, an effective amount of those selected from halide such as a brominated epoxy compound, tetrabromobisphenol A and a chlorinated paraffin, antimony trioxide, antimony pentaoxide, aluminum hydroxide, magnesium hydroxide, phosphate, polyphosphate and zinc borate as a flame retardant are added.
• halide such as a brominated epoxy compound, tetrabromobisphenol A and a chlorinated paraffin, antimony trioxide, antimony pentaoxide, aluminum hydroxide, magnesium hydroxide, phosphate, polyphosphate and zinc borate
• the method for production of the polymer solid electrolyte of the present invention is not specifically limited, but the polymer solid electrolyte can be normally produced by (1) a method of crosslinking a copolymer after mechanically mixing a copolymer and an electrolyte salt compound, or after mixing by dissolving a copolymer and an electrolyte salt compound in a solvent, followed by removal of the solvent; or (2) a method of crosslinking a copolymer, followed by mechanical mixing of the crosslinked copolymer and an electrolyte salt compound, or dissolving and mixing the crosslinked copolymer and an electrolyte salt compound in a solvent, and then removing the solvent.
• various kneaders As means for mechanically mixing, various kneaders, open roll, extruder, etc. can be optionally used.
• various polar solvents such as tetrahydrofuran, acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide, dioxane, methyl ethyl ketone and methyl isobutyl ketone may be used alone or in combination thereof.
• the concentration of the solution is not specifically limited, but it is preferably from 1 to 50% by weight.
• the amount of water used in the crosslinking reaction is not specifically limited because the crosslinking reaction easily occurs even in the presence of moisture in an atmosphere.
• the crosslinking can also be conducted by passing through a cold water or hot water bath for a short time, or exposing to a steam atmosphere.
• the crosslinking reaction is completed at the temperature of 10 to 200°C within 10 minutes to 20 hours.
• the crosslinking reaction when using a radical initiator, the crosslinking reaction is completed at the temperature of 10 to 200°C within 1 minutes to 20 hours. Furthermore, when using energy ray such as ultraviolet ray, a sensitizer is normally used. The crosslinking reaction is normally completed at the temperature of 10 to 150°C within 0.1 second to 1 hour. In case of the crosslinking agent having a silicon hydride, the crosslinking reaction is completed at the temperature of 10 to 180°C within 10 minutes to 10 hours.
• the copolymer of the present invention and the crosslinked material of the copolymer are a useful precursor for a polymer solid electrolyte.
• the polymer solid electrolyte is superior in mechanical strength and flexibility, and a large area thin-film shaped solid electrolyte can be easily obtained by utilizing the properties.
• a battery it is possible to make a battery by using the polymer solid electrolyte of the present invention.
• examples of a positive electrode material include lithium-manganese double oxide, lithium cobaltate, vanadium pentaoxide, polyacene, polypyrene, polyaniline, polyphenylene, polyphenylene sulfide, polyphenylene oxide, polypyrrole, polyfuran, and polyazulene.
• Examples of a negative electrode material include interlaminar compound prepared by occlusion of lithium between graphite or carbon layers, a lithium metal and a lithium-lead alloy.
• the crosslinked polymer solid electrolyte of the present invention can be used in a battery. By utilizing high ion conductivity, the crosslinked polymer solid electrolyte can also be used as a diaphragm of an ion electrode of the cation such as alkaline metal ion, Cu ion, Ca ion, and Mg ion.
• the polymer solid electrolyte of the present invention is particularly suitable as a material for electrochemical device such as a battery, a capacitor and a sensor.
• the composition (in terms of monomer) of the copolymer was analyzed by element analysis and 1 H NMR spectrum.
• the gel permeation chromatography measurement was conducted and the molecular weight was calculated in terms of standard polystyrene.
• the gel permeation chromatography measurement was conducted at 60°C by a measuring device RID-6A manufactured by Shimadzu Corp., using a column manufactured by Showa Denko such as Showdex KD-807, KD-806, KD-806M and KD-803, and a solvent DMF.
• the glass transition temperature and fusion heat were measured in a nitrogen atmosphere within the temperature range from -100 to 80°C at a heating rate of 10°C/min., using a differential scanning calorimeter DSC8230B manufactured by Rigaku Denki Co., Ltd.
• the measurement of the electrical conductivity ⁇ was conducted as follows. That is, a film vacuum-dried at 20°C under 1 mm Hg for 72 hours was sandwiched between platinum electrodes and the conductivity was calculated according to the complex impedance method, using an A.C. method (voltage: 0.5 V, frequency: 5 Hz to 1 MHz).
• the flexibility of the solid electrolyte film was evaluated by the presence or absence of breakage in case of folding the film at an angle of 180 degrees at 25°C.
• Tributyltin chloride (10 g) and tributyl phosphate (35 g) were charged in a three-necked flask equipped with a stirrer, a thermometer and a distillation device, and the mixture was heated at 250°C for 20 minutes while stirring under a nitrogen stream and the distillate was distilled off to obtain a solid condensate as a residue product.
• this condensate was used as a polymerization catalyst.
• the polymerization reaction was terminated by using methanol.
• the polymer was isolated by decantation, dried at 40°C under a normal pressure for 24 hours, and then dried at 45°C under reduced pressure for 10 hours to obtain 220 g of a polymer.
• the glass transition temperature of this copolymer was - 70°C, the number-average molecular weight was 400,000 and the fusion heat was 3 J/g. The results are shown in Table 1.
• the polyether copolymer (1 g) obtained in Example 1 and a catalyst dibutyltin dilaurate (5 mg) were dissolved in tetrahydrofuran (20 ml) and water (10 ⁇ l) was added, followed by stirring for 15 minutes. After the solvent was removed under a normal pressure, the mixture was dried at 60°C for 10 hours to obtain a crosslinked material.
• This crosslinked material was insoluble in an organic solvent, but it swelled in a solvent such as benzene and tetrahydrofuran.
• Example 7 The crosslinked material obtained in Example 7 (1 g) was impregnated with a tetrahydrofuran solution (5 ml) containing lithium perchlorate (100 mg) for 20 hours, heated and pressured at 160°C and 20 KgW/cm 2 for 10 minutes to obtain a film.
• This film had flexibility and its conductivity was 1.5 x 10 -4 S/cm at 20°C and 5.1 x 10 -4 S/cm at 60°C.
• the polyether copolymer (1 g) obtained in Examples 1 to 3 was dissolved in tetrahydrofuran (20 ml), and the resulting solution was mixed with a tetrahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05. Water was added to this mixed liquid under the condition that the amount in mol of water was three times that of the reactive silicon group-containing component. This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried, heated and pressured at 160°C and 20 KgW/cm 2 for 10 minutes to obtain a film. The results are shown in Table 2.
• the polyether copolymer (1 g) obtained in Examples 4 to 6 and a dibutyltin dilaurate catalyst (5 mg) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05 and water was added to this mixed solution in the same amount as that of the reactive silicon group-containing component.
• This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried and then allowed to stand at 100°C under an argon atmosphere for 3 hours to obtain a film.
• Table 2 The results are shown in Table 2.
• a copolymer having the structural units shown in Table 3 was synthesized in the same manner as in Example 1.
• Comparative Examples 1 and 3 a film was obtained in the same manner as in Example 9.
• Comparative Example 2 a film was obtained in the same manner as in Example 9, except for adding no water. The results were shown in Table 3.
• a lithium metal foil as the negative electrode and lithium cobaltate (LiCoO 2 ) as the positive electrode a secondary battery was prepared.
• the size of the crosslinked polymer solid electrolyte was 10 mm x 10 mm x 1 mm.
• the size of the lithium foil was 10 mm x 10 mm x 0.1 mm.
• Lithium cobaltate was prepared by mixing predetermined amounts of lithium carbonate and cobalt carbonate powder and then calcining the mixture at 900°C for 5 hours.
• the calcined mixture was ground, and then 12 parts by weight of acetylene black and 3 parts by weight of the crosslinked polymer solid electrolyte obtained in Example 9 were added to 85 parts by weight of the resulting lithium cobaltate, followed by mixing by a mortar and further press-molding under the pressure of 300 KgW/cm 2 to form a positive electrode having the size of 10 mm x 10 mm x 2 mm.
• the crosslinked polymer solid electrolyte obtained in Example 9 was sandwiched between the lithium metal foil and the lithium cobaltate plate, and the charge/discharge characteristics of the resulting battery were examined with applying the pressure of 10 KgW/cm 2 so that the interfaces were brought into contact with each other.
• the discharge current at the initial terminal voltage of 3.2 V was 0.4 mA/cm 2 and the charging could be conducted at 0.3 mA/cm 2 . It is possible to easily reduce the thickness of the battery in this Example and, therefore, a light-weight and large-capacity battery can be obtained.
• the polymerization reaction was conducted at 20°C for 8 hours.
• the polymerization reaction was terminated by using methanol.
• the polymer was isolated by decantation, dried at 40°C under a normal pressure for 24 hours, and then dried at 45°C under reduced pressure for 10 hours to obtain 195 g of a polymer.
• the glass transition temperature of this polymer was -70°C, the number-average molecular weight was 320,000 and the fusion heat was 3 J/g.
• the results of the composition analysis (in terms of monomer) of this polymer by 1 H NMR spectrum are as shown in Example 16 of Table 4.
• the polyether copolymer (1 g) obtained in Example 16 and diethylenetriamine (50 mg) were dissolved in tetrahydrofuran (20 ml), and then the reaction was conducted at 40°C for 2 hours. After the solvent was removed under reduced pressure, dried at 60°C for 6 hours to obtain a crosslinked material. This crosslinked material was insoluble in an organic solvent, but it swelled in a solvent such as benzene and tetrahydrofuran.
• the crosslinked material (1 g) obtained in Example 22 was impregnated with a tetrahydrofuran solution (5 ml) containing lithium perchlorate (100 mg) for 20 hours, heated and pressured at 160°C and 20 KgW/cm 2 for 10 minutes to obtain a film.
• This film had flexibility and its conductivity was 1.3 x 10 -4 S/cm at 20°C and 4.6 x 10 -4 S/cm at 60°C.
• the polyether copolymer (1 g) in Example 16 to 18 polymerized by using the organotin-phosphate ester condensate catalyst and maleic anhydride (150 mg) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05.
• This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried and then heated and pressured at 160°C and 20 KgW/cm 2 for one hour to obtain a film.
• Table 5 The results are shown in Table 5.
• the polyether copolymer (1 g) in Example 19 to 21 and diethylenetriamine (50 mg) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05.
• This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried and then allowed to stand at 100°C under an argon atmosphere for 10 hours to obtain a film.
• Table 2 The results are shown in Table 2.
• Example 16 Using the polyether copolymer shown in Table 6 obtained in the same manner as in Example 16, a film molding was conducted. In Comparative 4 and 6, a film was obtained in the same manner as in Example 24. In Comparative Example 5, a film molding was conducted as obtained in the same manner as in Example 9, except for adding no crosslinking agent.
• a lithium metal foil as the negative electrode and lithium cobaltate (LiCoO 2 ) as the positive electrode a secondary battery was prepared.
• the size of the crosslinked polymer solid electrolyte was 10 mm x 10 mm x 1 mm.
• the size of the lithium foil was 10 mm x 10 mm x 0.1 mm.
• Lithium cobaltate was prepared by mixing predetermined amounts of lithium carbonate and cobalt carbonate powder and then calcining the mixture at 900°C for 5 hours.
• the calcined mixture was ground, and then 12 parts by weight of acetylene black and 3 parts by weight of the crosslinked polymer solid electrolyte obtained in Example 24 were added to 85 parts by weight of the resulting lithium cobaltate, followed by mixing by a mortar and further press-molding under the pressure of 300 KgW/cm 2 to form a positive electrode having the size of 10 mm x 10 mm x 2 mm.
• Example 24 The crosslinked polymer solid electrolyte obtained in Example 24 was sandwiched between the lithium metal foil and the lithium cobaltate plate, and the charge/discharge characteristics of the resulting battery were examined with applying the pressure of 10 KgW/cm 2 so that the interfaces were brought into contact with each other.
• the discharge current at the initial terminal voltage of 3.2 V was 0.4 mA/cm 2 and the charging could be conducted at 0.3 mA/cm 2 . It is possible to easily reduce the thickness of the battery in this Example and, therefore, a light-weight and large-capacity battery can be obtained.
• the polyether copolymer (1 g) in Table 7 and 8 polymerized by using the organotin-phosphate ester condensate catalyst and dicumyl peroxide (a crosslinking agent) (0.015 g) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05.
• This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried and then heated and pressured at 160°C and 20 KgW/cm 2 for 10 minutes to obtain a film.
• the polyether copolymer (1 g) shown in Table 7 and 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane (a crosslinking agent) (0.02 g) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05.
• This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried and then heated and pressured at 145°C and 20 KgW/cm 2 for 10 minutes to obtain a film.
• the polyether copolymer (1 g) shown in Table 7 and benzoyl peroxide (a crosslinking agent) (0.02 g) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05.
• This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried and then heated and pressured at 80°C and 20 KgW/cm 2 for 5 hours to obtain a film.
• the polyether copolymer (1 g) shown in Table 7 and dicumyl peroxide (a crosslinking agent) (0.015 g) were dissolved in acetonitrile (20 ml), and the resulting solution was mixed with an acetonitrile solution of lithium bistrifluoromethanesulfonylimide so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05, and then a film was obtained in the same manner as in Examples 31 to 37.
• the polyether copolymer (1 g) shown in Table 7 and azobisisobutyronitrile (a crosslinking agent) (0.02 g) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05.
• This mixed liquid was casted on a mold made of polytetartluoroethylene, dried and then allowed to stand at 100°C under an argon atmosphere for 2 hours to obtain a film.
• the polyether copolymer (1 g) shown in Table 7 and 2,2-dimethoxy-1,2-diphenylethan-1-one (a sensitizer) (0.02 g) were dissolved in terahydrofuran (20 ml), and the resulting solution was mixed with a terahydrofuran solution of lithium perchlorate so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05.
• This mixed liquid was casted on a mold made of polytetartluoroethylene and dried, followed by ultraviolet ray irradiation (30 mW/cm 2 , 360 nm) under an argon atmosphere for 10 minutes to obtain a film.
• the polyether copolymer (1 g) shown in Table 7 and a polysiloxane (0.2 g) represented by the formula (11) were dissolved in toluene (10 ml) and an isopropyl alcohol solution containing 1% by weight of chloroplatinic acid was added, and the resulting solution was mixed with a toluene solution of lithium bistrifluoromethanesulfonylimide so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05, and then a film was obtained in the same manner as in Examples 31 to 37.
• Mn represents a number-average molecular weight (The same also in the following formulas (12) and (13)).
• the polyether copolymer (1 g) shown in Table 7 and a polysiloxane (0.2 g) represented by the formula (12) were dissolved in toluene (10 ml) and an isopropyl alcohol solution containing 1% by weight of chloroplatinic acid was added, and the resulting solution was mixed with a toluene solution of lithium bistrifluoromethanesulfonylimide so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05, and then a film was obtained in the same manner as in Examples 31 to 37.
• the polyether copolymer (1 g) shown in Table 7 and a polysiloxane (0.2 g) represented by the formula (13) were dissolved in toluene (10 ml) and an isopropyl alcohol solution containing 1% by weight of chloroplatinic acid was added, and the resulting solution was mixed with a toluene solution of lithium bistrifluoromethanesulfonylimide so that a molar ratio of the number of moles of the soluble electrolyte salt compound to the total number of moles of ethylene oxide units was 0.05, and then a film was obtained in the same manner as in Examples 31 to 37.
• Example 31 to 46 and Comparative Example 7 to 12 are described in Table 7 and 8.
• Table 7 and 8 the glass transition point and fusion heat were measured in a nitrogen atmosphere within the temperature range from -100 to 80°C at a heating rate of 10°C/min., using a differential scanning calorimeter DSC8230B manufactured by Rigaku Denki Co., Ltd.
• the measurement of the conductivity ⁇ was conducted as follows. That is, a film vacuum-dried at 20°C under 1 mm Hg for 72 hours was sandwiched between platinum electrodes and the conductivity was calculated according to the complex impedance method, using an A.C. method (voltage: 0.5 V, frequency: 5 Hz to 1 MHz).
• the flexibility of the solid electrolyte film was evaluated by the presence or absence of breakage in case of folding the film at an angle of 180 degrees.
• a lithium metal foil as the negative electrode and lithium cobaltate (LiCoO 2 ) as the positive electrode a secondary battery was prepared.
• the size of the crosslinked polymer solid electrolyte was 10 mm x 10 mm x 1 mm.
• the size of the lithium foil was 10 mm x 10 mm x 0.1 mm.
• Lithium cobaltate was prepared by mixing predetermined amounts of lithium carbonate and cobalt carbonate powder and then calcining the mixture at 900°C for 5 hours.
• the calcined mixture was ground, and then 12 parts by weight of acetylene black and 3 parts by weight of the crosslinked polymer solid electrolyte obtained in Example 33 were added to 85 parts by weight of the resulting lithium cobaltate, followed by mixing by a mortar and further press-molding under the pressure of 300 KgW/cm 2 to form a positive electrode having the size of 10 mm x 10 mm x 2 mm.
• the crosslinked polymer solid electrolyte obtained in Example 33 was sandwiched between the lithium metal foil and the lithium cobaltate plate, and the charge/discharge characteristics of the resulting battery were examined with applying the pressure of 10 KgW/cm 2 so that the interfaces were brought into contact with each other.
• the discharge current at the initial terminal voltage of 3.2 V was 0.4 mA/cm 2 and the charging could be conducted at 0.3 mA/cm 2 . It is possible to easily reduce the thickness of the battery in this Example and, therefore, a light-weight and large-capacity battery can be obtained.
• the polymer was isolated by decantation, dried at 40°C under a normal pressure for 24 hours, and then dried at 45°C under reduced pressure for 10 hours to obtain 298 g of a polymer.
• the composition (in terms of monomer) of the polymer by 1 H NMR spectrum and measurement of the bromine content was determined.
• the copolymer (1 g) obtained in Example 48, ethylene thiourea (a crosslinking agent) (0.015 g) and dibasic lead phthalate (0.05 g) were dissolved in acetonitrile (20 ml), and the resulting solution was mixed with an acetonitrile solution of lithium perchlorate so that a molar ratio of (the number of moles of the soluble electrolyte salt compound) to (the total number of moles of ethylene oxide units) was 0.07.
• This mixed liquid was casted on a mold made of polytetarfluoroethylene, dried and then heated and pressured at 170°C and 60 KgW/cm 2 for 15 minutes to obtain a film.
• the polymer solid electrolyte of the present invention is superior in processability, moldability, mechanical strength, flexibility, heat resistance and the like and the ionic conductivity is remarkably improved. Accordingly, it can be applied to electronic apparatuses such as a large-capacity condenser and a display device (e.g. an electrochromic display), including solid batteries.
• a display device e.g. an electrochromic display

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